CN104755427A - Method for producing composite oxide and composite oxide catalyst - Google Patents

Method for producing composite oxide and composite oxide catalyst Download PDF

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Publication number
CN104755427A
CN104755427A CN201380056367.9A CN201380056367A CN104755427A CN 104755427 A CN104755427 A CN 104755427A CN 201380056367 A CN201380056367 A CN 201380056367A CN 104755427 A CN104755427 A CN 104755427A
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aqueous solution
solution
cerium
composite
composite oxides
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CN104755427B (en
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松尾伸也
室田忠俊
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Santoku Corp
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Santoku Corp
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Abstract

Provided are a method and a catalyst for producing a composite oxide. The composite oxide shows a high conversion ratio of hydrogen carbide to hydrogen even after oxidation and is usable as a catalyst starting material with good handling properties. The aforesaid method comprises: a step (a) for preparing an aqueous Ce solution, in which 80 mol% or more of Ce ions are tetravalent, and an aqueous Zr solution containing Zr ions; a step (b1) for mixing a portion of the aqueous Ce solution with the aqueous Zr solution to give a mixed aqueous solution (X1); a step (c1) for hydrothermally treating the (X1); a step (b2) for adding the remainder of the aqueous Ce solution prepared in step (a) to a colloidal composite salt-containing solution (Y1) that is obtained in the step (c1) to give a colloidal composite salt-containing solution (Y2); a step (c2) for hydrothermally treating the (Y2) obtained in the step (b2); a step (d) for mixing a colloidal composite salt-containing solution (Y3) that is obtained in the step (c2), an aqueous alkali solution and a surfactant to give a precipitate; and a step (e) for baking the precipitate.

Description

For the preparation of method and the composite oxide catalysts of composite oxides
Technical field
The present invention relates to the method for the preparation of composite oxides, described composite oxides find the catalyzer being used as hydrocarbon steam reformation or waste-gas cleaning, and relate to the composite oxide catalysts containing these composite oxides.
Background technology
In order to suppress Global warming, recent active development has the fuel cell of high effciency of energy transfer.Polymer electrolyte fuel cells (PEFC) drops into actual family or vehicle uses.PEFC uses the oxygen in hydrogen and air to generate electricity as fuel, and hydrogen is by hydrocarbon, and the steam reformation as the hydrocarbon in city gas produces.Effective steam reformation needs catalyzer, and propose catalyzer as load Ru on alumina (non-patent literature 1), load Pt, Ru, Rh, Pd etc. (patent documentation 1) on the oxide solid solution of Zr, Ce and Fe or Y, and load is containing Pt, Rh, Ni, the Co etc. (patent documentation 2) on the oxide compound of Ce, Pr etc.
These catalyzer contain a large amount of precious metals, which increase the uncertainty of cost and supply.The oxidation of catalyzer makes hydrocarbon significantly be deteriorated to the reformation rate of hydrogen, makes the circumstance complication of process and operational conditions.
High cost for the Pt catalyzer of anode and negative electrode hampers the universalness of PEFC.Especially, a large amount of Pt catalyzer is used for the hydrogen reduction 1/2O at negative electrode 2+ 2H ++ 2e -→ H 2o.In this respect, the exploitation that can replace or reduce the catalystic material of the amount of Pt catalyzer is being carried out energetically.
As the catalyzer for purifying exhaust air used in vehicle, use so-called three-way catalyst, the carbon monoxide in waste gas and hydrocarbon are oxidized to carbon dioxide and water by it, reduction of nitrogen oxide are become nitrogen and water simultaneously.Three-way catalyst by such as catalytic metal Pt, Rh or Pd, and forms for promotor such as the Ce of the katalysis improving catalytic metal, described catalytic metal and the equal load of promotor in support of the catalyst as on aluminum oxide or trichroite.As mentioned above, the precious metal as such catalytic metal has problems at cost and supply side.
prior art document
Patent documentation 1:JP-2006-181473-A
Patent documentation 2:JP-2008-229604-A
Non-patent literature 1:IHI Engineering Review, Vol.45, No.3, p116-120 (2005-9)
summary of the invention
The object of this invention is to provide the method for the preparation of composite oxides and the composite oxide catalysts containing these composite oxides, described composite oxides are used as the catalyzer of hydrocarbon steam reformation or waste-gas cleaning, described method decreases the problem of above-mentioned catalyzer in cost and supply side, achieve the reformation rate of even high when being oxidized hydrocarbon to hydrogen, and be easy to process.
The present inventor conducts in-depth research to solve the problem, find in the preparation of the composite oxides containing Ce and Zr usually realized by a step hydrothermal treatment consists, before each hydrothermal treatment step, mix the part material cerium aqueous solution, this completes in two steps.By this program, obtain the composite oxides containing Ce and Zr, these composite oxides have specific degree of crystallinity and specific surface area, and compared with the oxide compound of routine, catalytic metal is more easily dispersed in wherein.In addition, by supported catalyst metal on the composite oxides obtained, obtain such catalyzer, it provides high hydrocarbon to the reformation rate of hydrogen, even and if also can keep high reformation rate when oxidised.Based on above discovery, complete the present invention.
According to the present invention, provide the method for the preparation of composite oxides, it comprises the following steps:
A cerium ion that () at least prepares 80 to 100mol% is the cerium aqueous solution of tetravalence, and the aqueous zirconium containing zirconium ion;
(b1) by the described aqueous zirconium of preparation in step (a) and the described cerium aqueous solution of part, to prepare mixed aqueous solution (X1);
(c1) mixed aqueous solution described in hydrothermal treatment consists (X1);
(b2) remainder of the described cerium aqueous solution of preparation in step (a) is joined the colloidal solution (Y1) of the composite salt obtained by the described hydrothermal treatment consists in step (c1), to prepare the colloidal solution (Y2) of composite salt;
(c2) colloidal solution (Y2) of described composite salt that obtained by step (b2) of hydrothermal treatment consists;
The colloidal solution (Y3) of d composite salt that () will be obtained by the described hydrothermal treatment consists in step (c2) mixes with basic solution and tensio-active agent, to prepare throw out; With
Throw out described in (e) roasting.
According to the present invention, additionally provide the composite oxides obtained by the method.
According to the present invention, further provide and comprise the composite oxide catalysts that these composite oxides and at least one are selected from the catalytic metal of Ni, Cu, Fe, Pt, Pd and Rh.
According to the present invention, further provide composite oxide catalysts, it is used for hydrocarbon steam reformation or waste-gas cleaning as catalyzer, and described composite oxide catalysts comprises the catalytic metal that above-mentioned composite oxides and at least one are selected from Ni, Cu, Fe, Pt, Pd and Rh.
Wherein in two independently step (b1) and (b2), the method for the preparation of composite oxides according to the present invention of the mixing cerium aqueous solution provides composite oxides with low cost in probabilistic situation of not supply, compared with conventional oxide, catalytic metal is more easily dispersed in described composite oxides.Method of the present invention additionally provides such composite oxides, its discovery uses in the catalyzer for hydrocarbon steam reformation or waste-gas cleaning, and when being used in catalyzer, it can realize the reformation rate of high hydrocarbon to hydrogen, and even when composite oxides are oxidized, also can keep high reformation rate.
To explain the present invention in detail now.
Method of the present invention comprises step (a): the cerium ion at least preparing 80 to 100mol% is the cerium aqueous solution of tetravalence, and the aqueous zirconium containing zirconium ion.
The cerium ion of 80 to 100mol% is the cerium aqueous solution of tetravalence, such as, cerous nitrate solution or ceric ammonium nitrate solution, preferably the former.
The starting point concentration of the cerium aqueous solution can be adjusted to according to CeO 2count usual 5 to 100g/l, preferably the cerium content of 10 to 80g/l.Concentration is too low to be caused poor efficiency and is industrially disadvantageous.
In step (a), the aqueous zirconium containing zirconium ion of preparation can be such as, the zirconium hydroxide aqueous solution, the zirconium chloride aqueous solution or the zirconium nitrate aqueous solution, preferred zirconyl nitrate solution.
Except the cerium aqueous solution and aqueous zirconium, step (a) optionally can comprise the rare earth metal aqueous solution of the ion containing rare earth metal except cerium except, and/or contains the preparation of the aqueous solution of ion of element (being hereafter sometimes referred to as element M) that at least one is selected from alkali earth metal, transition metal except Zr, haloid element, B, C, Si and S.
Total element in produced composite oxides beyond deoxygenation is by 100mol%, the aqueous solution of preparation is usually containing being not less than 10mol% and not higher than Ce or Ce of 90mol% and the mixture of other rare earth metals (being hereafter sometimes referred to as R) in the step (a), be not less than 10mol% and not higher than the Zr of 90mol%, or be not less than 0mol% and not higher than the M of 20mol%, preferably be not less than 50 and not higher than the R of 80mol%, be not less than 20mol% and not higher than the Zr of 50mol%, or be not less than 0mol% and not higher than the element M of 20mol%.
When R contains Pr, the content of Pr in R preferably not higher than 10mol%, more preferably not higher than 5mol%.
Zirconates industrially can contain the Hf of a few molar percentage, so that Hf is considered as being included in Zr herein.
Method of the present invention comprises step (b1): by the aqueous zirconium of preparation in step (a) and part cerium aqueous solution, to prepare mixed aqueous solution (X1).In this step, the rare earth metal aqueous solution of the ion containing the rare earth metal except cerium, and/or the aqueous solution of ion of element of alkali earth metal, transition metal except Zr, haloid element, B, C, Si and S is selected from containing at least one, can optionally be blended in mixed aqueous solution (X1).
Alkaline-earth metal can be, such as, and Mg, Ca, Sr or Ba; Rare earth metal in addition to Ce can be, such as, and Sc, Y, La, Nd, Pr or Tb; And the transition metal except Zr can be, such as, Ti, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Pd, Pt, Cu, Ag, Zn, Al, Ga, In, Ge, Sn or Bi.
In this step (b1), make the part cerium aqueous solution mix, and the remainder of the cerium aqueous solution is mixed in the step (b2) discussed following.The mass ratio carrying out the cerium aqueous solution part mixed in step (b1) and (b2) is preferably 0.1:99.9 to 30.0:70.0 quality %.Under ratio beyond this scope, the effect that the part of separating with two carries out the cerium aqueous solution mixed is not enough.
Method of the present invention comprises step (c1): hydrothermal treatment consists mixed aqueous solution (X1).
Hydrothermal treatment consists in step (c1) can be, such as, keep heating mixed aqueous solution (X1) to being not less than 60 DEG C.Heated by this maintenance, define the colloidal solution of cerium-zirconium composite salt.Operable reaction vessel can be sealing or uncovered container, and is preferably autoclave reactor.Keep the temperature of heating to be usually not less than 60 DEG C, be preferably 60 to 200 DEG C, be more preferably 80 to 180 DEG C.Keep the time length of heating to be generally 10 minutes to 48 hours, preferably 30 minutes to 36 hours, more preferably 1 is little of 24 hours.If keep heating under insufficient condition, degree of crystallinity does not raise, and the specific surface area of the final composite oxides produced and degree of crystallinity can not fall in the scope of hope.
Method of the present invention comprises step (b2): the colloidal solution (Y1) remainder of the cerium aqueous solution of preparation in step (a) being joined the composite salt obtained by hydrothermal treatment consists, to prepare the colloidal solution (Y2) of composite salt.In this step, the rare earth metal aqueous solution of the ion containing the rare earth metal except cerium, and/or the aqueous solution of ion of element of alkali earth metal, transition metal except Zr, haloid element, B, C, Si and S is selected from containing at least one, can optionally be blended in mixed aqueous solution (Y2).
Method of the present invention comprises step (c2): the colloidal solution (Y2) of hydrothermal treatment consists composite salt.
Hydrothermal treatment consists in step (c2) can be carried out according to the hydrothermal treatment consists in step (c1).
Method of the present invention comprises step (d): the colloidal solution (Y3) of the composite salt that will be obtained by the hydrothermal treatment consists in step (c2) is mixed with basic solution and tensio-active agent, to prepare throw out.
Step (d) is the neutralization procedure using basic solution, and described basic solution can be such as, and sodium hydroxide, potassium hydroxide, ammoniacal liquor or its mixture, particularly preferably be ammoniacal liquor.
Tensio-active agent can be such as, and anion surfactant is as ethoxy carboxylate, and nonionogenic tenside is as alcohol ethoxylate, and polyoxyethylene glycol, carboxylic acid or its mixture, particularly preferably be carboxylic acid.
Carboxylic acid can be preferably saturated carboxylic acid, as capric acid, lauric acid, tetradecanoic acid or palmitinic acid, particularly preferably is lauric acid.
Based on the composite oxides to be obtained of 100 mass parts, the amount of tensio-active agent to be added is generally 1 to 50 mass parts, is preferably 5 to 30 mass parts.When being less than 1 mass parts, the specific surface area of the final composite oxides produced and degree of crystallinity can not fall into the scope of hope.
Tensio-active agent can be worked as it and be used for during solid form, or when its be by by surfactivity dilution agent or be dissolved in solvent as ethanol or pure water in prepare solution form time use.Mixing can be carried out in known mixers.
The throw out obtained can by such as, and Nutsche method, centrifugal or press filtration are separated.Obtained throw out can be washed with water if desired.In addition, the precursor obtained can be dried to suitable degree.Drying can be carried out at about 60 to 200 DEG C.
Method of the present invention comprises step (e): the throw out that roasting obtains.
In step (e), can be prebake before roasting.The temperature of prebake is generally 250 to 700 DEG C, preferably 300 to 500 DEG C.Prebake can be carried out in air or oxygen.Compatibly can determine the time length of prebake according to prebake temperature, and can be 1 to 10 hour usually.
The composite oxides of prebake are pulverized, then roasting.Maturing temperature is generally 500 to 1200 DEG C, preferably 700 to 1100 DEG C, more preferably 800 to 1050 DEG C.Roasting can be carried out in air or oxygen, preferably oxygen.The time length of roasting compatibly can be determined according to maturing temperature, and can be 1 to 10 hour usually.
If desired, the composite oxides of acquisition can be ground into the particle diameter of hope.Such as, when being used as the composite oxides in hydrocarbon steam reforming catalyst, composite oxides preferably have the median size of 1 to 50 μm.
The composite oxides obtained can be selected from the catalytic metal of Ni, Cu, Fe, Pt, Pd and Rh by load at least one, be prepared into the catalyzer of hope.Catalytic metal can pass through conventional method load on composite oxides, such as, by the aqueous impregnation composite oxides with catalytic metal, and then roasting.Maturing temperature is generally 250 to 800 DEG C, is preferably 300 to 600 DEG C.Roasting can be carried out in air or oxygen, preferably oxygen.The time length of roasting compatibly can be determined according to maturing temperature, and can be 1 to 10 hour usually.
Namely catalyzer more according to the present invention can show catalytic performance after baking, but can carry out activation treatment if desired, as reduction and/or oxidation.
Usually the composite oxides advantageously obtained by method of the present invention when used as a catalyst, have larger specific surface area.In addition, contriver finds, and the higher degree of crystallinity of the composite oxides of supported catalyst metal obtains more effective catalytic performance.Therefore, the present inventor has adopted the composite oxides with high-crystallinity, wherein keeps specific surface area large as far as possible.Such composite oxides on microcosmic by two or more closely similar CaF 2or similar formation mutually, and think because the boundary oxygen at such phase patibhaga-nimitta is absorbed securely and moves reposefully thus reduction catalysts metal, therefore show good catalytic performance.When composite oxides have above-mentioned composition, specific surface area and degree of crystallinity, preferably form two or more closely similar CaF 2or similar phase, to show good catalytic performance.
Catalyzer of the present invention preferably provides and is not less than 40%, the methane being preferably not less than 80% is to the reformation rate of hydrogen, as catalyzer being heated to 600 DEG C from room temperature by flowing down at oxygen in 1.5 hours, at 600 DEG C, keep catalyzer 1 hour, and measure that methane steam reforming measures.
Methane steam reforming as referred to herein can measure under condition discussed below.
The mensuration of methane steam reforming can start like this: measure 50.0mg catalyzer and be fixed on by catalyzer in the fixed bed reaction pipe (internal diameter 11mm) be made up of silica glass, by catalyzer above and remain on below between quartz glass cotton.Then make hydrogen flow in reaction tubes with 100ml/min, in 1.5 hours, pipe is heated to 600 DEG C from room temperature simultaneously.Described pipe, when reaching 600 DEG C, makes it keep 1 hour with reducing catalyst.After reduction, stop hydrogen, and nitrogen is introduced so that hydrogen is emptying from pipe.After thorough emptying hydrogen, use nitrogen is as carrier gas and methane and water are 1:3, nitrogen, methane gas and water vapour is introduced in reaction tubes respectively, and start to measure the reformation rate of methane to hydrogen with 90ml/min, 2.5ml/min and 7.5ml/min.Measurement is carried out as follows: to sampling four times of working off one's feeling vent one's spleen, and every minor tick 13 minutes, often plants sample gas by gas chromatographic analysis, and average.This program is called measurement (1).
After measurement (1), make oxygen flow into reaction tubes with 100ml/min, and holding tube 1 hour is with oxide catalyst.Then stop oxygen, and introduce nitrogen with oxygen emptying from pipe.After thorough emptying oxygen, measure the reformation rate of methane to hydrogen in the mode identical with measuring (1).This program is called measurement (2).
After measurement (2), make hydrogen flow into reaction tubes with 100ml/min, and holding tube 1 hour is with reducing catalyst.After reduction, stop hydrogen, and introduce nitrogen with hydrogen emptying from pipe.After thorough emptying hydrogen, measure the reformation rate of methane to hydrogen in the mode identical with measuring (1).This program is called measurement (3).
After measurement (3), with 90ml/min, nitrogen is flowed in reaction tubes, temperature is reduced to room temperature simultaneously.Then, make in oxygen inflow pipe with 100ml/min, in 1.5 hours, temperature is increased to up to 600 DEG C from room temperature simultaneously.When temperature reaches 600 DEG C, holding tube 1 hour is with oxide catalyst.After oxidation, stop oxygen, and introduce nitrogen with oxygen emptying from pipe.After thorough emptying oxygen, measure the reformation rate of methane to hydrogen in the mode identical with measuring (1).This program is called measurement (4).
After measurement (4), make hydrogen flow into reaction tubes with 100ml/min, and holding tube 1 hour is with reducing catalyst.After reduction, stop hydrogen, and introduce nitrogen with hydrogen emptying from pipe.After thorough emptying hydrogen, measure the reformation rate of methane to hydrogen in the mode identical with measuring (1).This program is called measurement (5).
Be used in the methane (CH measured in gas-chromatography 4), carbonic acid gas (CO 2) and the value of carbon monoxide (CO), calculate reformation rate as follows.
Reformation rate (%)=(1-CH 4/ (CH 4+ CO 2+ CO)) × 100
Catalyst according to the invention can be used as PEFC, substitute for the Pt catalyzer in the catalyzer etc. of purifying exhaust air, and preferably can be used as hydrocarbon steam reforming catalyst.
Embodiment
Explain the present invention now with reference to embodiment and comparative example, it is not intended to limit the present invention.
embodiment 1
Be the cerous nitrate aqueous solution of tetravalence and zirconyl nitrate solution and praseodymium nitrate aqueous solution by the cerium ion that the part (5 overall quality %) of preparation is not less than 90%, to obtain the constituent ratio of 12.0mol%Ce, 80.0mol%Zr and 8.0mol%Pr, the mixing solutions of the 886ml being 8.7g/l with oxide basis concentration with preparation, and the mixing solutions of acquisition is placed in the separatory flask of 1 liter.Separatory flask is equipped with agitator and Dimroth prolong, hydrothermal treatment consists mixing solutions 8 hours at 98 DEG C, is cooled to room temperature to obtain the colloidal solution (Y1) of cerium-zirconium-praseodymium composite salt.
The remainder (95 overall quality %) that the cerium ion being not less than 90% is the cerous nitrate aqueous solution of tetravalence is added in the solution (Y1) of the composite salt so obtained, to obtain the constituent ratio of 73.2mol%Ce, 24.4mol%Zr and 2.4mol%Pr, with prepare 1 liter with the colloidal solution (Y2) of the oxide basis concentration cerium-zirconium-praseodymium composite salt that is 30.5g/l.With the colloidal solution (Y2) 20 hours with mode identical above composite salt that hydrothermal treatment consists so obtains at 98 DEG C, and be cooled to room temperature to obtain the colloidal solution (Y3) of cerium-zirconium-praseodymium composite salt.
Under agitation the solution (Y3) of composite salt is joined in the basic solution prepared by 12.5% ammoniacal liquor 23.7g ammonium laurate being dissolved in 315ml, to obtain the precursor of the composite oxides of gel form with 50ml/min.Gel is filtered and washs to obtain filter cake, prebake filter cake 5 hours at 400 DEG C, then roasting 3 hours in oxygen at 1000 DEG C.Use ICP to measure the composite oxides so obtained, find when Ce, Zr and Pr add up to 100mol%, constituent ratio is 73.2mol%Ce, 24.4mol%Zr and 2.4mol%Pr.Afterwards, composite oxides are flooded so that when Ce, Zr and Pr add up to 100mol% with nickelous nitrate and Palladous nitrate, there is 5.00mol%Ni and 1.25mol%Pd as catalytic metal, and at 500 DEG C in oxygen roasting 3 hours to obtain composite oxides.The described composite oxides using icp analysis so to obtain, find that, when Ce, Zr and Pr add up to 100mol%, Ni and Pd content is respectively 5.00mol% and 1.25mol%.
The catalyzer of the composite oxides of acquisition like this carries out the mensuration of methane steam reforming as discussed above.Result display in Table 1.
embodiment 2 to 6
Except maturing temperature and the change as shown in table 1 of Ni and Pd content, composite oxides and catalyzer are prepared in the same manner as example 1.The catalyzer obtained carries out methane steam reforming mensuration.Result display in Table 1.
comparative example 1
Be the aqueous solution of the cerous nitrate of tetravalence and zirconium hydroxide and praseodymium nitrate aqueous solution by the cerium ion being not less than 90%, to obtain the constituent ratio of 73.2mol%Ce, 24.4mol%Zr and 2.4mol%Pr, to prepare the mixing solutions being 30g/l with oxide basis concentration of 1 liter, and the mixing solutions of acquisition is placed in the separatory flask of 1 liter.Separatory flask is equipped with agitator and Dimroth prolong, and at 98 DEG C, keep heating 20 hours.After maintenance heating, flask is cooled to room temperature to obtain the colloidal solution of cerium-zirconium-praseodymium composite salt.Under agitation with 50ml/min, the solution of composite salt is added in 12.5% ammoniacal liquor of 415ml, to obtain the precursor of the composite oxides of gel form.Gel is filtered and washs to obtain filter cake.Add to obtained filter cake the 3g ammonium laurate that is dissolved in pure water and mix.Then at 400 DEG C prebake mixture 5 hours to obtain composite oxides.The composite oxides of roasting acquisition in oxygen at 1000 DEG C 3 hours.Measure the composite oxides produced with ICP, find that constituent ratio is 73.2mol%Ce, 24.4mol%Zr and 2.4mol%Pr.
With the aqueous impregnation composite oxides of nickelous nitrate so that when Ce, Zr and Pr add up to 100mol%, there is 6.25mol%Ni, and at 500 DEG C in oxygen roasting 3 hours to obtain catalyzer.With the described composite oxides that icp analysis so obtains, find when Ce, Zr and Pr add up to 100mol%, Ni content is 6.25mol%.
As discussed above the catalyzer obtained is carried out to the mensuration of methane steam reforming.Result display in Table 1.
comparative example 2 to 4
Except maturing temperature change as shown in table 1, prepare composite oxides and catalyzer in the mode identical with embodiment 2 to 4.The catalyzer obtained is carried out to the mensuration of methane steam reforming.Result display in Table 1.
comparative example 5 to 7
Except zirconium hydroxide is replaced by the aqueous solution of Zircosol ZN, and beyond maturing temperature and the change as shown in table 1 of Ni and Pd content, composite oxides are prepared in the mode identical with comparative example 1 with catalyzer.The catalyzer obtained is carried out to the mensuration of methane steam reforming.The results are shown in table 1.
embodiment 7
Be the cerous nitrate aqueous solution of tetravalence and zirconyl nitrate solution and praseodymium nitrate aqueous solution by the cerium ion that the part (5 whole quality %) of preparation is not less than 90%, to obtain the constituent ratio of 4.3mol%Ce, 87.0mol%Zr and 8.7mol%Pr, the mixing solutions of the 919ml being 16.0g/l with oxide basis concentration with preparation, and the mixing solutions of acquisition is placed in the separatory flask of 1 liter.Separatory flask is equipped with agitator and Dimroth prolong, hydrothermal treatment consists mixing solutions 8 hours at 98 DEG C, is cooled to room temperature to obtain the colloidal solution (Y1) of cerium-zirconium-praseodymium composite salt.
The remainder (95 overall quality %) that the cerium ion being not less than 90% is the cerous nitrate aqueous solution of tetravalence is added in the solution (Y1) of the composite salt so obtained, to obtain the constituent ratio of 47.6mol%Ce, 47.6mol%Zr and 4.8mol%Pr, with prepare 1 liter with the colloidal solution (Y2) of the oxide basis concentration cerium-zirconium-praseodymium composite salt that is 30.8g/l.With the colloidal solution (Y2) 20 hours with mode identical above composite salt that hydrothermal treatment consists so obtains at 98 DEG C, and be cooled to room temperature to obtain the colloidal solution (Y3) of cerium-zirconium-praseodymium composite salt.
Under agitation the solution (Y3) of composite salt is joined in the basic solution prepared by 12.5% ammoniacal liquor 23.7g ammonium laurate being dissolved in 315ml, to obtain the precursor of the composite oxides of gel form with 50ml/min.Gel is filtered and washs to obtain filter cake, prebake filter cake 5 hours at 400 DEG C, then roasting 3 hours in oxygen at 1000 DEG C.Use ICP to measure the composite oxides so obtained, find when Ce, Zr and Pr add up to 100mol%, constituent ratio is 47.6mol%Ce, 47.6mol%Zr and 4.8mol%Pr.Afterwards, composite oxides are flooded so that when Ce, Zr and Pr add up to 100mol% with nickelous nitrate and Palladous nitrate, there is 5.00mol%Ni and 1.25mol%Pd as catalytic metal, and at 500 DEG C in oxygen roasting 3 hours to obtain composite oxides.The described composite oxides using icp analysis so to obtain, find that, when Ce, Zr and Pr add up to 100mol%, Ni and Pd content is respectively 5.00mol% and 1.25mol%.The catalyzer of the composite oxides of acquisition like this carries out the mensuration of methane steam reforming as discussed above.Result display in table 2.
embodiment 8 to 13
Except maturing temperature and the change as shown in table 2 of Ni and Pd content, composite oxides are prepared in the mode identical with embodiment 7 with catalyzer.The catalyzer obtained carries out methane steam reforming mensuration.Result display in table 2.
comparative example 8
Be the aqueous solution of the cerous nitrate of tetravalence and zirconium hydroxide and praseodymium nitrate aqueous solution by the cerium ion being not less than 90%, to obtain the constituent ratio of 47.6mol%Ce, 47.6mol%Zr and 4.8mol%Pr, to prepare the mixing solutions being 30g/l with oxide basis concentration of 1 liter, and the mixing solutions of acquisition is placed in the separatory flask of 1 liter.Separatory flask is equipped with agitator and Dimroth prolong, and at 98 DEG C, keep heating 20 hours.After maintenance heating, flask is cooled to room temperature to obtain the colloidal solution of cerium-zirconium-praseodymium composite salt.Under agitation with 50ml/min, the solution of composite salt is added in 12.5% ammoniacal liquor of 415ml, to obtain the precursor of the composite oxides of gel form.Gel is filtered and washs to obtain filter cake.Add to obtained filter cake the 3g ammonium laurate that is dissolved in pure water and mix.Then at 400 DEG C prebake mixture 5 hours to obtain composite oxides.The composite oxides of roasting acquisition in oxygen at 1000 DEG C 3 hours.Measure the composite oxides produced with ICP, find that constituent ratio is 47.6mol%Ce, 47.6mol%Zr and 4.8mol%Pr.
With the aqueous impregnation composite oxides of nickelous nitrate so that when Ce, Zr and Pr add up to 100mol%, there is 6.25mol%Ni, and at 500 DEG C in oxygen roasting 3 hours to obtain catalyzer.With the described composite oxides that icp analysis so obtains, find when Ce, Zr and Pr add up to 100mol%, Ni content is 6.25mol%.
As discussed above the catalyzer obtained is carried out to the mensuration of methane steam reforming.Result display in table 2.
comparative example 9 to 12
Except maturing temperature change as shown in table 2, prepare composite oxides and catalyzer in the mode identical with 9 to 11 with embodiment 7.The catalyzer obtained is carried out to the mensuration of methane steam reforming.Result display in table 2.
comparative example 13 and 14
Except maturing temperature and the change as shown in table 2 of Ni and Pd content, prepare composite oxides and catalyzer in the mode identical with comparative example 8.The catalyzer obtained is carried out to the mensuration of methane steam reforming.Result display in table 2.

Claims (7)

1. prepare a method for composite oxides, it comprises the following steps:
A cerium ion that () at least prepares 80 to 100mol% is the cerium aqueous solution of tetravalence, and the aqueous zirconium containing zirconium ion;
(b1) by the described aqueous zirconium of preparation in step (a) and the described cerium aqueous solution of part, to prepare mixed aqueous solution (X1);
(c1) mixed aqueous solution described in hydrothermal treatment consists (X1);
(b2) remainder of the described cerium aqueous solution of preparation in step (a) is joined the colloidal solution (Y1) of the composite salt obtained by the described hydrothermal treatment consists in step (c1), to prepare the colloidal solution (Y2) of composite salt;
(c2) colloidal solution (Y2) of described composite salt that obtained by step (b2) of hydrothermal treatment consists;
The colloidal solution (Y3) of d composite salt that () will be obtained by the described hydrothermal treatment consists in step (c2) mixes with basic solution and tensio-active agent, to prepare throw out; With
Throw out described in (e) roasting.
2. method according to claim 1, wherein step (a) also comprises the rare earth metal aqueous solution of the ion of preparation containing the rare earth metal except cerium, and
Wherein by the described mixed aqueous solution (X1) of described rare earth metal aqueous solution in step (b1), or in the colloidal solution (Y2) of described composite salt in step (b2), or in both.
3. method according to claim 1 and 2, wherein step (a) also comprises preparation is selected from alkali earth metal, transition metal except Zr, haloid element, B, C, Si and S aqueous solution of ion of element containing at least one, and
Wherein by the described mixed aqueous solution (X1) of described aqueous solution in step (b1), or in the colloidal solution (Y2) of described composite salt in step (b2), or in both.
4. the method according to any one of claims 1 to 3, the cerium aqueous solution wherein added in step (b1) is 0.1:99.9 to 30.0:70.0 quality % with the mass ratio of the cerium aqueous solution added in step (b2).
5. composite oxides, its method according to any one of Claims 1-4 obtains.
6. a composite oxide catalysts, it comprises the catalytic metal that composite oxides according to claim 5 and at least one are selected from Ni, Cu, Fe, Pt, Pd and Rh.
7. composite oxide catalysts according to claim 6, it is used for hydrocarbon steam reformation or waste-gas cleaning as catalyzer.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109529802A (en) * 2018-11-12 2019-03-29 山东国瓷功能材料股份有限公司 A kind of cerium zirconium compound oxide and its preparation method and application

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20180345255A1 (en) * 2015-11-30 2018-12-06 Santoku Corporation Steam reforming catalyst for hydrocarbons
CN110270321A (en) * 2019-07-04 2019-09-24 南京大学 The preparation method and its product of a kind of cerium Si composite oxide and application
US11358128B2 (en) 2019-12-30 2022-06-14 Saudi Arabian Oil Company High activity reforming catalyst formulation and process for low temperature steam reforming of hydrocarbons to produce hydrogen
KR102255059B1 (en) * 2020-01-30 2021-05-24 창원대학교 산학협력단 Method for preparing high efficiency ceria catalyst for air pollution purification using hydrothermal synthesis

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101444740A (en) * 2008-12-16 2009-06-03 中国科学院广州能源研究所 Catalyst for hydrogen production by bio-oil steam reforming and preparation method thereof
US20130210617A1 (en) * 2010-07-07 2013-08-15 Rhodia Operations Composition based on oxides of cerium, of niobium and, optionally, of zirconium and use thereof in catalysis

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU779487B2 (en) 1999-08-17 2005-01-27 Battelle Memorial Institute Chemical reactor and method for catalytic gas phase reactions
US6864214B2 (en) * 2000-09-26 2005-03-08 Daihatsu Motor Co., Ltd. Exhaust gas purifying catalyst
FR2852591B1 (en) 2003-03-18 2006-06-16 Rhodia Elect & Catalysis COMPOSITION BASED ON ZIRCONIUM OXIDE AND CERIUM OXIDE AT MAXIMUM TEMPERATURE OF REDUCED REDUCIBILITY, PROCESS FOR PREPARING THE SAME AND USE THEREOF AS CATALYST
KR20040100136A (en) 2003-05-21 2004-12-02 한화석유화학 주식회사 Method for doping metal oxides
JP4296430B2 (en) 2004-12-27 2009-07-15 戸田工業株式会社 Catalyst for water gas shift reaction and process for producing the same
JPWO2007142116A1 (en) * 2006-06-05 2009-10-22 日産化学工業株式会社 Method for producing metal oxide particles
JP4831753B2 (en) * 2006-06-13 2011-12-07 株式会社豊田中央研究所 Exhaust gas purification catalyst
US8883865B2 (en) 2006-09-05 2014-11-11 Cerion Technology, Inc. Cerium-containing nanoparticles
US10435639B2 (en) 2006-09-05 2019-10-08 Cerion, Llc Fuel additive containing lattice engineered cerium dioxide nanoparticles
JP5428103B2 (en) 2007-02-21 2014-02-26 国立大学法人 大分大学 Catalyst for low-temperature hydrogen production, its production method and hydrogen production method
WO2009101984A1 (en) * 2008-02-12 2009-08-20 Santoku Corporation Composite oxide
EP2285737A2 (en) * 2008-04-22 2011-02-23 Basf Se Method for prereforming ethanol
JP4979087B2 (en) * 2008-04-23 2012-07-18 株式会社豊田中央研究所 Composite oxide powder, production method and production apparatus thereof, and exhaust gas purification catalyst
FR2936515B1 (en) 2008-09-30 2011-08-05 Saint Gobain Ct Recherches ZIRCONIUM OXIDE POWDER
AU2008365234B2 (en) * 2008-12-17 2015-05-07 Cerion, Llc Fuel additive containing lattice engineered cerium dioxide nanoparticles
US8679344B2 (en) 2008-12-17 2014-03-25 Cerion Technology, Inc. Process for solvent shifting a nanoparticle dispersion
US8017097B1 (en) * 2010-03-26 2011-09-13 Umicore Ag & Co. Kg ZrOx, Ce-ZrOx, Ce-Zr-REOx as host matrices for redox active cations for low temperature, hydrothermally durable and poison resistant SCR catalysts

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101444740A (en) * 2008-12-16 2009-06-03 中国科学院广州能源研究所 Catalyst for hydrogen production by bio-oil steam reforming and preparation method thereof
US20130210617A1 (en) * 2010-07-07 2013-08-15 Rhodia Operations Composition based on oxides of cerium, of niobium and, optionally, of zirconium and use thereof in catalysis

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
齐延等: ""尿素基水热共沉淀法铈锆固溶体的制备及应用"", 《中国稀土学报》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109529802A (en) * 2018-11-12 2019-03-29 山东国瓷功能材料股份有限公司 A kind of cerium zirconium compound oxide and its preparation method and application
CN109529802B (en) * 2018-11-12 2021-12-28 山东国瓷功能材料股份有限公司 Cerium-zirconium composite oxide and preparation method and application thereof

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